WO2019124556A1 - Copolymère de polycarbonate-polydiorganosiloxane, composition de résine de copolymère de polycarbonate-polydiorganosiloxane, et procédé de production d'une composition de résine de copolymère de polycarbonate-polydiorganosiloxane - Google Patents

Copolymère de polycarbonate-polydiorganosiloxane, composition de résine de copolymère de polycarbonate-polydiorganosiloxane, et procédé de production d'une composition de résine de copolymère de polycarbonate-polydiorganosiloxane Download PDF

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WO2019124556A1
WO2019124556A1 PCT/JP2018/047367 JP2018047367W WO2019124556A1 WO 2019124556 A1 WO2019124556 A1 WO 2019124556A1 JP 2018047367 W JP2018047367 W JP 2018047367W WO 2019124556 A1 WO2019124556 A1 WO 2019124556A1
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group
carbon atoms
resin composition
copolymer
polydiorganosiloxane
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PCT/JP2018/047367
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English (en)
Japanese (ja)
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太一 木村
丹藤　和志
晃司 小田
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帝人株式会社
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Priority to CN201880076044.9A priority Critical patent/CN111386298B/zh
Priority to EP18890638.2A priority patent/EP3730534B1/fr
Priority to KR1020207015107A priority patent/KR102321244B1/ko
Priority to US16/956,041 priority patent/US11414523B2/en
Priority to JP2019560601A priority patent/JP7055152B2/ja
Publication of WO2019124556A1 publication Critical patent/WO2019124556A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes

Definitions

  • the present invention relates to a polycarbonate-polydiorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer”) or a resin composition, and a method for producing the resin composition. More particularly, the present invention relates to a PC-POS copolymer or resin composition having excellent impact resistance, particularly impact resistance and chemical resistance at extremely low temperatures, and a method of producing the resin composition.
  • PC-POS copolymer polycarbonate-polydiorganosiloxane copolymer
  • Polycarbonate is widely used in the fields of optical components, electric and electronic devices, and automobiles because it is excellent in impact resistance and high in heat resistance. Furthermore, in order to cope with the recent expansion of the field of application, development of a copolycarbonate in which various copolymerization monomer units are introduced into a general monomer raw material such as bisphenol A (hereinafter abbreviated as BPA) has been promoted. Among them, PC-POS copolymers comprising BPA and polydiorganosiloxane comonomers are known to be excellent in flame retardancy and impact resistance, and many documents are disclosed (Patent Documents 1 to 3).
  • Patent Documents 4 to 5 As a method of improving the impact resistance of a PC-POS copolymer, particularly at low temperatures, a method of using a long polydiorganosiloxane focusing on the chain length in the polydiorganosiloxane structure used is disclosed (Patent Documents 4 to 5).
  • Patent Document 6 focuses on the size of a siloxane domain formed in a molded product, and appropriately blends two types of PC-POS copolymers having different light transmittances to obtain a certain level of transparency and resistance. A method of achieving both impact is disclosed.
  • Patent Document 7 discloses a method for producing a resin composition containing a PC-POS copolymer starting from a polydiorganosiloxane having a long chain length and a polydiorganosiloxane having a short chain length. The example which made impact resistance compatible is shown.
  • the resin compositions containing PC-POS copolymer or PC-POS copolymer up to now are all impact resistant, especially at extremely low temperatures assumed to high places such as high latitudes and mountain areas.
  • the performance in impact resistance is insufficient, and a resin composition containing PC-POS copolymer or PC-POS copolymer which is compatible with high chemical resistance and coating durability can not be obtained. .
  • PC-POS copolymer alone can not obtain high flame retardancy such as V-0 based on UL standard 94. Therefore, there is a method of blending a flame retardant with this PC-POS copolymer in order to obtain high flame retardancy (Patent Documents 2 and 8). However, thin-walled flame retardancy can not be said to be sufficient by these methods.
  • Patent Documents 9 and 10 methods of adding polytetrafluoroethylene particles and a flame retardant to polycarbonate are known (Patent Documents 9 and 10). However, these documents do not describe that very high flame retardancy and low temperature impact properties can be obtained by selecting a specific PC-POS copolymer as a polycarbonate resin.
  • An object of the present invention is to provide a polycarbonate-polydiorganosiloxane copolymer or resin composition having excellent impact resistance, in particular, impact resistance at low temperature and chemical resistance.
  • the above copolymer comprising the polycarbonate-polydiorganosiloxane copolymer and an optional polycarbonate resin, or the resin composition thereof,
  • the copolymer comprises (A-1) a polycarbonate block, and (A-2) a polydiorganosiloxane block,
  • the (A-2) polydiorganosiloxane block is contained in the copolymer or the resin composition thereof in an amount of 2.5 to 8.0% by weight, and the following (i) and (ii) Said copolymer or its resin composition to be filled:
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 carbon atoms
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to 20 carbon atoms.
  • An aryl group of to 14, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7).
  • ⁇ Configuration 5 The copolymer or the resin composition thereof as described in any one of constitutions 1 to 4, wherein the viscosity average molecular weight is 11,000 to 30,000.
  • the (A-1) polycarbonate block is derived from 2,2-bis (4-hydroxyphenyl) propane, and the (A-2) polydiorganosiloxane block is a (2-allylphenol) -terminated polydiorgano. Derived from siloxane or (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane, The copolymer according to any one of constitutions 1 to 5, or a resin composition thereof.
  • ⁇ Configuration 7 The copolymer according to any one of constitutions 1 to 6, or its resin composition, comprising 100 to 1% by weight of the copolymer and 0 to 99% by weight of the polycarbonate resin.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to 20 carbon atoms.
  • An aryl group of to 14, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7).
  • Structure 11 The resin composition as described in structure 9 or 10 which further contains (C) a fluorine-containing anti-dropping agent and / or (D) a ultraviolet absorber.
  • ⁇ Configuration 12 A molded article formed from the copolymer according to any one of constitutions 1 to 7, or the resin composition thereof, or the resin composition according to constitutions 8 to 11.
  • Water-insoluble organic solvent is 8 to less than 9.5 moles per 1 mole of the total amount of dihydric phenols represented by the formula [4] and the formula [5] and after initiating the interfacial polycondensation reaction, it is further insoluble in water
  • the PC-POS copolymer of the present invention or the resin composition thereof has excellent impact resistance, particularly impact resistance and chemical resistance at extremely low temperatures, and also has high coating durability.
  • the industrial effects to be played are exceptional.
  • tool It is a figure of a 3 point
  • tool It is a figure of a 3 point
  • tool is a figure of a 3 point
  • the PC-POS copolymer of the present invention comprises (A-1) a polycarbonate block and (A-2) a polydiorganosiloxane block.
  • the resin composition of the present invention is a resin composition containing the above-mentioned copolymer, and preferably comprises 100 to 1% by weight of a PC-POS copolymer and 0 to 99% by weight of a polycarbonate resin.
  • the content of the (A-2) polydiorganosiloxane block is 2.5 to 8.0% by weight, and the following (i) and (ii) Meet): (I) 1 to 20 domains having a maximum major axis of 80 nm or more exist in an area of 850 nm square (722,500 nm 2 ) in a cross-sectional observation image of a resin composition using an electron microscope; and (ii) an average domain 30 ⁇ 100 nm in size.
  • PC-POS co-polymers by reacting polydiorganosiloxanes with carbonate oligomers having terminal chloroformate groups at very high concentrations, as has not previously been done. It is found that it is possible to form coarse domains of 80 nm or more while forming domains of a specific average size in the polymer, and the dispersion state of such domains is the impact resistance of the PC-POS copolymer ( In particular, they have been found to be very advantageous in impact resistance at very low temperatures.
  • a combination of a PC-POS copolymer and a polycarbonate resin may be abbreviated as A component.
  • the PC-POS copolymer comprises (A-1) polycarbonate block and (A-2) polydiorganosiloxane block, preferably (A-1) polycarbonate block of the formula [1] and formula It contains a polydiorganosiloxane block of (A-2) of [3].
  • the (A-1) polycarbonate block is a part based on polycarbonate contained in the PC-POS copolymer, and the type thereof is not particularly limited.
  • such polycarbonate based moieties may be aromatic polycarbonate based moieties.
  • the (A-1) polycarbonate block is represented by the following formula [1].
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 14 carbon atoms, aryloxy groups having 6 to 14 carbon atoms, carbon atoms 7-20 aralkyl group, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, if .R 1 and R 2 represents a group selected from the group consisting of cyano group and a carboxyl group is more people each May be the same or different.
  • alkyl group having 1 to 18 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and tetradecyl group. .
  • it is an alkyl group having 1 to 6 carbon atoms.
  • alkoxy group having 1 to 18 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group and an octoxy group.
  • Alkyl groups having 1 to 6 carbon atoms are preferred.
  • Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl. Preferred is a cycloalkyl group having 6 to 12 carbon atoms. Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyloxy. Preferred is a cycloalkyl group having 6 to 12 carbon atoms.
  • alkenyl group having 2 to 10 carbon atoms examples include methenyl group, ethenyl group, propenyl group, butenyl group and pentenyl group.
  • Alkyl groups having 1 to 6 carbon atoms are preferred.
  • Examples of the aryl group having 6 to 14 carbon atoms include phenyl group and naphthyl group.
  • Examples of the aryloxy group having 6 to 14 carbon atoms include phenyloxy and naphthyloxy.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenylethyl group.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy and phenylethyloxy.
  • e and f are each independently an integer of 1 to 4; W is at least one group selected from the group consisting of a single bond or a group represented by the following formula [2]. )
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon It represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms.
  • alkyl group having 1 to 18 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group.
  • it is an alkyl group having 1 to 6 carbon atoms.
  • Examples of the aryl group having 6 to 14 carbon atoms include phenyl group and naphthyl group. These may be substituted.
  • Examples of the substituent include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl and butyl.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenylethyl group.
  • R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a carbon atom A cycloalkoxy group having 6 to 20 atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, It represents a group selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. When there are plural, they may be the same or different.
  • alkyl group having 1 to 18 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and tetradecyl group. .
  • it is an alkyl group having 1 to 6 carbon atoms.
  • alkoxy group having 1 to 10 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
  • Alkyl groups having 1 to 6 carbon atoms are preferred.
  • Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl. Preferred is a cycloalkyl group having 6 to 12 carbon atoms.
  • Examples of the cycloalkoxy group having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyl. Preferred is a cycloalkyl group having 6 to 12 carbon atoms.
  • alkenyl group having 2 to 10 carbon atoms examples include methenyl group, ethenyl group, propenyl group, butenyl group and pentenyl group.
  • Alkyl groups having 1 to 6 carbon atoms are preferred.
  • Examples of the aryl group having 6 to 14 carbon atoms include phenyl group and naphthyl group.
  • Examples of the aryloxy group having 6 to 14 carbon atoms include phenyloxy and naphthyloxy.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenylethyl group.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy and phenylethyloxy.
  • g is an integer of 1 to 10, preferably an integer of 1 to 6; h is an integer of 4 to 7, preferably an integer of 4 to 5.
  • the polycarbonate block represented by the formula [1] is preferably a block derived from 2,2-bis (4-hydroxyphenyl) propane.
  • the length of the polycarbonate block is preferably 10 to 100, more preferably 30 to 100, still more preferably 50 to 70, as the average number of repeating units of the formula [1].
  • the content of the polycarbonate block is preferably 50 to 99.9% by weight, more preferably 70 to 99.% by weight based on the total weight of the copolymer. It is 5% by weight, more preferably 80 to 99.0% by weight.
  • the copolymer of the present invention contains a polydiorganosiloxane block, and the content of the polydiorganosiloxane block in the copolymer or resin composition is 2.5 to 8.0% by weight.
  • the polydiorganosiloxane block is represented by the following formula [3].
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons, or a substitution or 6 to 12 carbons It is an unsubstituted aryl group.
  • alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group.
  • it is an alkyl group having 1 to 6 carbon atoms.
  • substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group.
  • substituents examples include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl. It is preferable that R 3 , R 4 , R 5 , R 6 , R 7 and R 8 be a methyl group.
  • R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl.
  • it is an alkyl group having 1 to 6 carbon atoms.
  • alkoxy group having 1 to 10 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group and an octoxy group.
  • it is an alkyloxy group having 1 to 6 carbon atoms.
  • p is a natural number
  • q is 0 or a natural number
  • the average chain length p + q is a natural number of 30 to 100.
  • the average chain length p + q is preferably 35 to 90, more preferably 50 to 70.
  • p is preferably 35 to 90, more preferably 50 to 70.
  • q is preferably 0 to 80, more preferably 0 to 50.
  • X is a divalent aliphatic group having 2 to 8 carbon atoms.
  • the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms.
  • alkylene group include ethylene group, trimethylene group and tetramethylene group.
  • the polydiorganosiloxane block represented by the above formula [3] is preferably a block derived from (2-allylphenol) -terminated polydiorganosiloxane or (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane . That is, in the formula [3], it is preferable that X is a trimethylene group and R 9 and R 10 are hydrogen atoms, or that X is a trimethylene group and R 9 and R 10 are a methoxy group.
  • the content of the polydiorganosiloxane block in the copolymer or resin composition of the present invention is 2.5 to 8.0% by weight
  • the PC-POS copolymer is a resin of the present invention
  • the PC-POS copolymer can have a polydiorganosiloxane block at a content different from this range.
  • the content of the polydiorganosiloxane block, in particular the content of the polydiorganosiloxane block represented by the above [3], is, for example, 3.0 to 30.0 weight based on the total weight of the PC-POS copolymer %, 3.5 to 20.0% by weight, or 4.0 to 15.0% by weight.
  • the PC-POS copolymer when contained in the resin composition of the present invention, 4.0 to 70.0 wt%, 8.0 to 60.0 wt% of the PC-POS copolymer, It may be 10.0 to 30.0% by weight, or 12.0 to 25.0% by weight. Within such a range, maximum domain formation is possible, low-temperature impact resistance can be exhibited, and since an emulsified state can be formed, a polymerization reaction can be performed, and the glass transition temperature is appropriate. Therefore, it has advantages in production, such as granulation.
  • the viscosity average molecular weight of the copolymer is preferably 5.0 ⁇ 10 3 to 3.5 ⁇ 10 4 , more preferably 1.0 ⁇ 10 4 to 2.5 ⁇ 10 4 , still more preferably 1.2 ⁇ 10 4 It is 4 to 2.0 ⁇ 10 4 , particularly preferably 1.5 ⁇ 10 4 to 1.8 ⁇ 10 4 . If the viscosity average molecular weight of the copolymer is less than the lower limit, practical mechanical strength is hardly obtained in many fields, and the melt viscosity difference with the polycarbonate resin etc. to be mixed is large, and the kneadability is deteriorated. Since the melt viscosity is high and generally requires a high molding processing temperature, defects such as thermal deterioration of the resin and productivity deterioration due to separation failure in the water washing process at the time of production tend to be caused.
  • the type of the polycarbonate resin optionally contained in the resin composition of the present invention is not particularly limited as long as the advantageous effects of the present invention can be provided.
  • the polycarbonate resin may be, for example, a polycarbonate comprising (A-1) a polycarbonate block which does not contain the (A-2) polydiorganosiloxane block as described above, and the polycarbonate resin may be represented by the following general formula [4] It may be derived from dihydric phenol (I) represented by For example, as the dihydric phenol, for example, 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) ) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclo
  • 1,1-bis (4-hydroxyphenyl) -1-phenylethane 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene, 1,4-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene is preferred, in particular 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis ( - hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-bis (4-
  • the copolymer and resin composition of the present invention consist of 100 to 1% by weight of PC-POS copolymer and 0 to 99% by weight of polycarbonate.
  • the content of the polydiorganosiloxane block in the present invention is 2.5 to 8.0 wt%, 3.0 to 7.0 wt% based on the resin composition (particularly, only the resin weight of the resin composition). Preferably, 3.5 to 6.5 wt% is more preferred.
  • the amount is less than the lower limit, sufficient low temperature impact resistance is not expressed, and when the amount is more than the upper limit, the appearance (color unevenness, peeling failure) is deteriorated, the rigidity is lowered, the glass transition temperature is lowered, the thermal bending resistance is lowered, etc. Poor in physical properties.
  • the viscosity average molecular weight of the above resin composition is preferably 11,000 to 30,000, and more preferably 12,000 to 25,000. When it is smaller than 11,000, sufficient low temperature impact resistance does not appear, and when it is larger than the upper limit value, productivity decrease due to increase in solution viscosity and insufficient molding fluidity occur.
  • the PC-POS copolymer in the present invention has an aggregated structure in which polydiorganosiloxane domains are dispersed in a matrix of polycarbonate polymer.
  • the polydiorganosiloxane domain in this invention means the domain which has the polydiorganosiloxane disperse
  • the polydiorganosiloxane domain is not necessarily composed of a single component because the structure is formed by phase separation with the polycarbonate matrix.
  • the maximum major axis is 80 nm or more in the 850 nm square (722,500 nm 2 ) region. There are 1 to 20, preferably 2 to 20, more preferably 4 to 20, and most preferably 5 to 20 organosiloxane domains.
  • the maximum major axis is 80 nm or more and no polydiorganosiloxane domain is present, sufficient cryogenic impact resistance does not appear, and when 20 or more, the appearance is deteriorated (color unevenness, peeling defect), and cryogenic impact Sex also decreases.
  • no polydiorganosiloxane domain having a maximum major axis of 400 nm or more is present in any of the five sample sections in the 850 nm square (722,500 nm 2 ) region.
  • the maximum major axis is at least 400 nm but no polydiorganosiloxane domain exists, but when one or more of these exist, the appearance (color unevenness, peeling defect) and chemical resistance Both sex tend to decrease. Moreover, when it is out of these ranges, it may deteriorate also about a flame retardance.
  • the average size of the polydiorganosiloxane domain in the present invention is 30 to 100 nm or more than 45 nm and 100 nm or less, preferably 40 to 80 nm, more preferably 50 to 70 nm.
  • the lower limit of the average size is preferably 30 nm, more preferably 40 nm, and particularly preferably 50 nm.
  • the upper limit of the average size is preferably 100 nm, more preferably 80 nm, particularly preferably 70 nm. If it is less than the lower limit of this range, impact resistance and chemical resistance are not sufficiently exhibited, and if the upper limit of this range is exceeded, the appearance is deteriorated (color unevenness, peeling failure) and the chemical resistance is also reduced.
  • the largest major axis of the polydiorganosiloxane domain of the copolymer molded article in the present invention is evaluated in a cross-sectional observation image of a 850 nm square (722,500 nm 2 ) resin composition using an electron beam microscope.
  • the average domain size of the polydiorganosiloxane domains of the copolymer molded article in the present invention means the number average of individual domain sizes.
  • the terms "maximum major axis of domain” and “average domain size” indicate measured values obtained by cutting thin sections from 4.0 mm thick molded pieces formed by injection molding and observing them by TEM.
  • a section of 15 mm is cut from the gate of the molded piece at room temperature using a microtome, and the magnification is determined by TEM. The observation is performed at 20,000 times, and the obtained TEM photograph is subjected to image analysis software Win ROOF Ver. Particle analysis was performed using 6.6 (Mitani Shoji Co., Ltd.) to obtain the average size and particle size distribution (frequency distribution) of the polydiorganosiloxane domains in the sample flakes.
  • each domain the maximum major axis (length when any two points on the outer contour of the particle were selected so as to maximize the length between them) was used. Similar analysis is performed on five sample sections, and the average value is taken as the value of each sample.
  • polydiorganosiloxane having a specific average chain length is used as a raw material. That is, it is represented by hydroxyaryl-terminated polydiorganosiloxane (II) represented by the following general formula [5], and the average chain length p + q is 30 to 100, preferably 35 to 90, and more preferably 50 to 70. preferable.
  • II hydroxyaryl-terminated polydiorganosiloxane
  • two or more different hydroxy aryl-terminated polydiorganosiloxane (II) raw materials having different average chain length p + q may be mixed and prepared.
  • a polydiorganosiloxane (X-1) having an average chain length p + q of 1 to less than 60 and a polydiorganosiloxane (X-2) having an average chain length p + q of 60 to 200 are used as raw materials.
  • polydiorganosiloxanes having an appropriate average chain length before hydroxy aryl modification of the ends even by a method of mixing appropriate polydiorganosiloxane raw materials with hydroxy aryl modification of the ends.
  • either method may be used to modify the terminal with hydroxyaryl.
  • the average chain length p + q of the polydiorganosiloxane block in the PC-POS copolymer obtained by reacting the polydiorganosiloxane raw material with a dihydric phenol and a polycarbonate precursor is preferably 30 to 100, more preferably as described above. Is 35 to 90, more preferably 50 to 70.
  • the average chain length p + q is calculated by nuclear magnetic resonance (NMR) measurement.
  • the weight ratio of (X-1) to (X-2) is 1:99 to 99: 1. Is more preferably used in a ratio of 10:90 to 90:10.
  • polydiorganosiloxane raw material polydiorganosiloxane (X) obtained by previously blending the above polydiorganosiloxanes (X-1) and (X-2), and the blending ratio is as described above Similar to the X-1) :( X-2) mass ratio, the mass ratio is preferably 1:99 to 99: 1, more preferably 10:90 to 90:10.
  • the lower limit of the average chain length p + q of the polydiorganosiloxane (X-1) is preferably 1 or more, more preferably 20 or more, still more preferably 30 or more, and the upper limit is Preferably it is less than 60, more preferably less than 50, still more preferably less than 45.
  • the lower limit of the average chain length p + q of the polydiorganosiloxane (X-2) is preferably 60 or more, more preferably 70 or more, still more preferably 90 or more, and the upper limit is preferably 200 or less. And more preferably 100 or less.
  • the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [5] for example, the following compounds are suitably used.
  • the hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol Can be easily prepared by hydrosilylation of the end of the polysiloxane chain having a predetermined degree of polymerization.
  • (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and in particular (2-allylphenol) -terminated polydimethylsiloxane, (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxanes are preferred.
  • PC-POS copolymer in the present invention can be produced by the steps (a) and (b).
  • dihydric phenol (I) and the like are precursors capable of producing a polycarbonate block
  • dihydric phenol (II) and the like can produce a polydiorganosiloxane block. It is a precursor.
  • step (a) dihydric phenol (I) represented by the following formula [4] is reacted with phosgene in a mixture of an organic solvent insoluble in water and an aqueous alkali solution to have a terminal chloroformate group It is a process of preparing a solution containing a carbonate oligomer.
  • dihydric phenol (I) represented by the formula [4] for example, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene and 1,4-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene are preferred.
  • 2,2-bis (4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis (4-hydroxy) -3-Methylphenyl) fluorene is preferred.
  • 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable.
  • the PC-POS copolymer of the present invention As a method for producing the PC-POS copolymer of the present invention, it is effective to react polydiorganosiloxane at a high concentration with a carbonate oligomer having terminal chloroformate group to form a coarse domain of 80 nm or more. Thus, it is possible to develop an unconventional dispersed state in the region where the content of siloxane blocks is low.
  • polydiorganosiloxane having a specific average chain length may be used as a raw material, and only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.
  • a raw material represented by hydroxyaryl-terminated polydiorganosiloxane (II) represented by the following general formula [5] and having an average chain length p + q of 30 to 100 is used.
  • two or more different hydroxy aryl-terminated polydiorganosiloxane (II) raw materials having an average chain length p + q may be mixed and used.
  • polydiorganosiloxane (X-1) having an average chain length p + q of 1 to less than 60 and polydiorganosiloxane (X-2) having an average chain length p + q of 60 to 200 are used as raw materials.
  • the polydiorganosiloxane (X-1) and the polydiorganosiloxane (X-2) may be blended in advance, without parallel blending.
  • the reaction solution may be charged, or (X-1) and (X-2) may be divided and sequentially added to the reaction solution to react with the carbonate precursor and the dihydric phenol.
  • the polydiorganosiloxane (X-1) is charged into the reaction solution, and then the polydiorganosiloxane (X-2) is charged into the reaction solution to react with the carbonate precursor and the dihydric phenol. It is desirable from the viewpoint of forming a domain of 80 nm or more which contributes to the improvement of efficiency and cost by simplification of the manufacturing process and the improvement of impact resistance.
  • the final introduction of the polydiorganosiloxane (X-2) alone facilitates the local introduction of a polydiorganosiloxane block having a large average chain length into the polymer chain, and is advantageous for domain formation of 80 nm or more.
  • polydiorganosiloxane (X-1) to (X-2) used as the raw material is as described above, and the carbonate precursor and the dihydric phenol will be described later.
  • the total amount 1 mol of dihydric phenols represented by [4] and the formula [5] is preferably 8 to less than 11 moles, and more preferably 8 to 9.5 moles.
  • the total amount of the dihydric phenol means the total amount of bisphenol which is a raw material of polycarbonate and a polydiorganosiloxane monomer.
  • the amount of the insoluble organic solvent is the total amount used up to the time when the catalyst is added to start the polycondensation reaction, and the amount used in the production of the polycarbonate oligomer, polydiorganosiloxane monomer and end terminator
  • the amount used for dissolution is the total amount of the amount added to adjust the state of emulsification during interfacial polycondensation reaction.
  • the organic solvent insoluble in water per mole of the total of dihydric phenols represented by [4] and formula [5] is less than the lower limit. Deterioration of the emulsified state during polymerization lowers the polymer quality, and the solution viscosity is too high, so the productivity also decreases, and when it exceeds the upper limit, domain formation of 80 nm or more is insufficient and extremely low temperature impact resistance is not expressed . Furthermore, after the reaction of the carbonate precursor and the dihydric phenol with the polydiorganosiloxane proceeds, a water-insoluble organic solvent may be added immediately.
  • the water-insoluble organic solvent is represented by the formula [4] and the formula [5] It is desirable to add 2 moles or more per mole of the total amount of the dihydric phenol represented. Thereby, it is possible to suppress the deposition risk of the polymer component due to the high concentration while securing a sufficient degree of reaction progress.
  • a mixture containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (I) and a carbonate-forming compound in advance in a mixture of an organic solvent insoluble in water and an aqueous alkaline solution Prepare a solution.
  • the entire amount of dihydric phenol (I) used in the method of the present invention may be oligomerized at once, or a part thereof may be used as a post addition monomer in the subsequent interface.
  • the post-addition monomer is added to accelerate the subsequent polycondensation reaction, and it is not necessary to add it if not necessary.
  • the system of this oligomer formation reaction is not specifically limited, Usually, the system performed in a solvent in the presence of an acid binder is preferable.
  • the use ratio of the carbonate ester forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ
  • the acid binder examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.
  • the use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of an acid binder based on the number of moles of dihydric phenol (I) used for formation of the oligomer (usually 1 mole is equivalent to 2 equivalents) .
  • solvents inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent.
  • Representative examples include, for example, hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like.
  • halogenated hydrocarbon solvents such as methylene chloride are suitably used.
  • the reaction pressure of the oligomer formation is not particularly limited and may be normal pressure, elevated pressure or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure.
  • the reaction temperature is selected from the range of -20 ° C to 50 ° C, and in many cases, it is desirable to be cooled with water or ice because it generates heat during polymerization.
  • the reaction time depends on other conditions and can not be generally defined, but is usually 0.2 to 10 hours.
  • the pH range of the oligomerization reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or more.
  • the present invention thus obtains a mixed solution containing an oligomer of dihydric phenol (I) having terminal chloroformate groups, and then stirring the mixed solution while stirring the hydroxyaryl-terminated polydiorganosiloxane (II).
  • the PC-POS copolymer is obtained by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.
  • an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.
  • hydroxyaryl-terminated polydiorganosiloxane (II) used or a part of the dihydric phenol (I) as described above is added to this reaction step as a post-addition monomer, It is preferable to use two equivalents or more of an alkali relative to the total number of moles of the phenol (I) having a hydroxyl group and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually one mole corresponds to 2 equivalents).
  • the polycondensation by the interfacial polycondensation reaction of the dihydric phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.
  • terminal terminators or molecular weight regulators are usually used.
  • the terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols and aliphatic carboxylic acids Chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like are exemplified. The amount thereof is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination is there.
  • a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.
  • the reaction time of such polymerization reaction needs to be relatively long in order to reduce unreacted polydiorganosiloxane components. Preferably it is 30 minutes or more, More preferably, it is 50 minutes or more. On the other hand, since precipitation of the polymer may occur by stirring the reaction solution for a long time, it is preferably 180 minutes or less, more preferably 90 minutes or less.
  • an antioxidant such as sodium sulfite or hydrosulfide may be added.
  • the copolymer of the present invention can be made into a branched copolymer by using a branching agent in combination with the above-mentioned dihydric phenol compound.
  • the trifunctional or higher polyfunctional aromatic compound used for the branched copolymer is phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- ⁇ 4- Trisphenol such as [1,1-bis (4-hydroxyphenyl) ethyl] benzen
  • the reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but it can usually be suitably carried out under normal pressure or about the self-pressure of the reaction system.
  • the reaction temperature is selected from the range of -20 ° C to 50 ° C, and in many cases, it is desirable to be cooled with water or ice because it generates heat during polymerization.
  • the reaction time varies depending on other conditions such as the reaction temperature and can not be generally specified, but it is usually performed in 0.5 to 10 hours.
  • the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain the desired reduced viscosity [ ⁇ SP It can also be obtained as a polycarbonate copolymer of / c].
  • the resulting reaction product (crude product) can be subjected to various post treatments such as known separation and purification methods, and recovered as a PC-POS copolymer of desired purity (purification degree).
  • PC-POS copolymer of the present invention can be blended with various flame retardants, reinforcing fillers, and additives which are blended in a general polycarbonate resin composition as long as the effects of the present invention are not impaired.
  • ⁇ B component flame retardant>
  • various compounds conventionally known as flame retardants of thermoplastic resins, particularly aromatic polycarbonate resins can be applied, and more preferably (b1) an organic metal salt type Flame retardants (for example, organic sulfonic acid alkali (earth) metal salts, metal salts of boric acid salt flame retardants, and metal tinate flame retardants, etc.
  • an organic metal salt type Flame retardants for example, organic sulfonic acid alkali (earth) metal salts, metal salts of boric acid salt flame retardants, and metal tinate flame retardants, etc.
  • organophosphorus flame retardants for example, monophosphate compounds, phosphate oligomers
  • a silicone-based flame retardant comprising a silicone compound
  • the compounding of the compound used as a flame retardant improves only the flame retardancy Not, based on the nature of each compound, for example, the improvement of antistatic properties, flowability, stiffness and thermal stability It is brought about.
  • the content of the component B is 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, and more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the component A. If the content of the component B is less than 0.001 part by weight, flame retardancy can not be maintained, and if it exceeds 20 parts by weight, impact resistance and flame retardancy can not be satisfied.
  • the organic metal salt flame retardant is advantageous in that the heat resistance is substantially maintained.
  • the organic metal salt flame retardant most preferably used in the present invention is a metal salt of an alkali (earth) metal sulfonate.
  • alkali (earth) metal salts of fluorine-substituted organic sulfonic acids are preferable, and alkali (earth) metal salts of sulfonic acids having a perfluoroalkyl group are particularly preferable.
  • the carbon number of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8.
  • the metal constituting the metal ion of the fluorine-substituted organic sulfonic acid alkali (earth) metal salt is an alkali metal or alkaline earth metal, and examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium, and alkaline earth
  • the class metals include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Therefore, the preferred organic metal salt flame retardant is a perfluoroalkylsulfonic acid alkali metal salt.
  • alkali metals rubidium and cesium are preferable when transparency is required to be high, but they are not versatile and difficult to purify, and as a result, they may be disadvantageous in terms of cost. is there. On the other hand, although it is advantageous in cost and flame retardancy, lithium and sodium may be disadvantageous in transparency.
  • the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used in consideration of these, a potassium perfluoroalkylsulfonic acid salt is most preferable in any point of which the balance of characteristics is excellent.
  • Such a potassium salt and a perfluoroalkylsulfonic acid alkali metal salt consisting of another alkali metal can also be used in combination.
  • Such perfluoroalkyl sulfonic acid alkali metal salts include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluorobutane sulfone Sodium acid, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexanesulfonate, rubidium perfluorobutanesulf
  • the content of fluoride ions measured by the ion chromatography method is preferably 50 ppm or less, more preferably 20 ppm or less, and still more preferably 10 ppm or less.
  • the lower the fluoride ion content the better the flame retardancy and the light resistance.
  • the lower limit of the fluoride ion content can be substantially zero, but in view of the balance between the number of purification steps and the effect, about 0.2 ppm is preferable practically.
  • the perfluoroalkylsulfonic acid alkali metal salt having such a fluoride ion content is purified, for example, as follows.
  • the perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of ion exchange water of the metal salt in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.).
  • the perfluoroalkylsulfonic acid alkali metal salt is a method of neutralizing a perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or using a perfluoroalkylsulfonyl fluoride as an alkali metal carbonate or hydroxide. It is produced by a method of neutralization (more preferably by the latter method).
  • the ion-exchanged water is particularly preferably water having an electric resistance value of 18 M ⁇ ⁇ cm or more.
  • the solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the solution is cooled to a range of 0 to 40 ° C., more preferably 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.
  • a fluorine-substituted organic sulfonic acid alkali (earth) metal salt is used as a flame retardant
  • the amount thereof is preferably 0.01 to 1.0 parts by weight, more preferably 0 based on 100 parts by weight of component A.
  • the content is from 0.5 to 0.8 parts by weight, more preferably from 0.08 to 0.6 parts by weight.
  • the effect expected by the mixing
  • an organic metal salt flame retardant other than the fluorine-substituted organic sulfonic acid alkali (earth) metal salt a metal salt of an organic sulfonic acid not containing a fluorine atom is preferable.
  • the metal salt include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids Also contains no fluorine atom).
  • aliphatic sulfonic acid metal salts include alkali metal (alkyl earth) metal salts, which may be used alone or in combination of two or more (here, alkali The notation of (earth) metal salt is used in the meaning including both an alkali metal salt and an alkaline earth metal salt).
  • alkanesulfonic acid used for such alkylsulfonic acid alkali (earth) metal salts include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptane Sulfonic acid, octane sulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more.
  • aromatic sulfonic acid used for the aromatic sulfonic acid alkali (earth) metal salt a sulfonic acid of monomeric or polymeric aromatic sulfide, a sulfonic acid of aromatic carboxylic acid and ester, monomeric or polymeric Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfone sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Mention may be made of at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides, and condensation products of methylene sulfonic groups of aromatic sulfonic acids, and these may be used alone or in combination of two or more. be able to.
  • aromatic sulfonate alkaline (earth) metal salt examples include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysulfonate polysodium Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Potassium, lithium poly (2-fluoro-6-buty
  • alkali (earth) metal salts of aromatic sulfonic acids are preferred, and potassium salts are particularly preferred.
  • aromatic sulfonic acid alkali (earth) metal salt is blended as a flame retardant, its content is preferably 0.01 to 1 part by weight, more preferably 0 based on 100 parts by weight of the component A.
  • the content is from 0.5 to 0.8 parts by weight, more preferably from 0.08 to 0.6 parts by weight.
  • phosphate compounds in particular aryl phosphate compounds are suitable.
  • Such phosphate compounds are effective in improving the flame retardancy, and since the phosphate compounds have a plasticizing effect, they have a decrease in heat resistance, but they are advantageous in that they can enhance the molding processability of the resin composition of the present invention. It is.
  • various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or two or more phosphate compounds represented by the following general formula [6] can be mentioned particularly.
  • Y represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-methylcyclohexane, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis A dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of (4-hydroxyphenyl) sulfide; g, h, i and j each independently represent 0 or 1, and n is 0 to 5
  • R 21, R 22, R 23, and R 24 are each independently phenol, cresol, xylen
  • dihydric phenol which derives Y of the above formula [6] are resorcinol, bisphenol A, and dihydroxy diphenyl, among which resorcinol and bisphenol A are particularly preferable.
  • Preferred specific examples of the monohydric phenol for deriving R 21 , R 22 , R 23 and R 24 in the above formula [6] are phenol, cresol, xylenol, and 2,6-dimethylphenol, and among these, phenol is preferable. And 2,6-dimethylphenol.
  • phosphate compound of the above formula [6] mainly include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bis (2,6-xylyl) phosphate) Phosphate oligomers, phosphate oligomers based on 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphoric acid ester oligomers based on bisphenol A bis (diphenyl phosphate) are preferred, among which resorcinol bis di (2,6- Phosphate oligomers based on xylyl) phosphate), Phosphate oligomers based on 4, 4-dihydroxydiphenyl bis (diphenyl phosphate), and bisphenol A bis (dipheny) Phosphoric acid ester oligomer composed mainly of phosphate) are preferable.
  • monophosphate compounds such as triphenyl phosphate and tri (2,6-
  • organophosphorus flame retardants include phosphazene.
  • the phosphazene can impart flame retardancy to the resin composition by containing a phosphorus atom and a nitrogen atom in the molecule.
  • the phosphazene is not particularly limited as long as it is a compound which does not contain a halogen atom and has a phosphazene structure in the molecule.
  • the phosphazene compounds are represented by the general formulas [7] and [8].
  • R 25 , R 26 , R 27 and R 28 each represent a hydrogen, a hydroxyl group, an amino group or an organic group not containing a halogen atom, and n represents an integer of 3 to 10).
  • the formula [7], in [8], as the organic group containing no R 25, R 26, R 27 , and halogen atom represented by R 28 is, for example, an alkoxy group, a phenyl group, an amino group, an allyl group Etc.
  • cyclic phenoxy phosphazene represented by the following general formula [9] is preferable.
  • the blending amount thereof is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, still more preferably 3 to 10 with respect to 100 parts by weight of component A. It is a weight part.
  • the effect anticipated by the mixing
  • the silicone compound of the present invention is not particularly limited as long as the flame retardancy and transparency which are the object of the present invention can be obtained, but a silicone compound having an aromatic group is preferred, and the viscosity at 25 ° C is 300 cSt or less. preferable. When the viscosity is high, the transparency of the molded article may be reduced. Furthermore, in order for the silicone compound to exhibit the flame retardant effect efficiently, the dispersed state in the combustion process is important. An important factor in determining such dispersion state is viscosity.
  • the viscosity at 25 ° C. is more preferably 10 to 300 cSt, still more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt, from such a viewpoint considered to be difficult to form a structure.
  • the aromatic group possessed by the silicone compound is bonded to the silicone atom, which contributes to the improvement of the compatibility with polycarbonate and the maintenance of transparency, and is also advantageous for the formation of a carbonized film at the time of combustion, so it is flame retardant It also contributes to the manifestation of the effect.
  • it does not have an aromatic group it is difficult to obtain the transparency of the molded article, and it tends to be difficult to obtain a high degree of flame retardancy.
  • the silicone compound of the present invention is preferably a silicone compound containing a Si-H group.
  • it is a silicone compound containing Si—H group and aromatic group in the molecule, (1)
  • the amount of Si-H group contained is 0.1 to 1.2 mol / 100 g (2) 10 to 70% by weight of a ratio (aromatic group weight) containing an aromatic group represented by the following general formula [10],
  • X each independently represents an OH group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group.
  • M 1 represents an integer of 0 to 5. Furthermore, the formula is In [10], when m1 is 2 or more, different types of X can be taken from each other.
  • Average degree of polymerization is 3 to 150 It is more preferable that it is at least one or more silicone compounds selected from silicone compounds which are More preferably, it is selected from silicone compounds containing a structural unit represented by at least one or more of structural units represented by the following general formulas [11] and [12] as a Si—H group-containing unit At least one silicone compound.
  • Z 1 to Z 3 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group, or a general formula 13 represents a compound represented by the formula 13.
  • ⁇ 1 to ⁇ 3 each independently represent 0 or 1.
  • m2 represents an integer of 0 or 1.
  • the repeating unit in the case of m2 of 2 or more is It is possible to take multiple repeating units different from each other.
  • Z 4 to Z 8 each independently represent a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group.
  • ⁇ 4 to ⁇ 8 each independently represent 0 Or represents 1.
  • m3 represents an integer of 0 or 1.
  • repeating units can take a plurality of repeating units different from each other. More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, it is a silicone compound comprising MD units or MDT units.
  • the hydrocarbon group 20 include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and decyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl and allyl, and phenyl And aryl groups such as tolyl group and aralkyl groups, and these groups may contain various functional groups such as epoxy group, carboxyl group, carboxylic acid anhydride group, amino group, and mercapto group. Good.
  • it is an alkyl group having 1 to 8 carbon atoms, an alkenyl group or an aryl group, and particularly preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group or a propyl group, a vinyl group or a phenyl group.
  • constituent units represented by the general formulas [11] and [12] in the silicone compound containing a constituent unit represented by at least one or more formulas, when having a repeating unit of a plurality of siloxane bonds, they are random co It is also possible to take any form of polymerization, block copolymerization and tapered copolymerization.
  • the amount of Si-H in the silicone compound is preferably in the range of 0.1 to 1.2 mol / 100 g.
  • the amount of Si-H is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated at the time of combustion.
  • they are silicone compounds having an Si—H content in the range of 0.1 to 1.0 mol / 100 g, and most preferably in the range of 0.2 to 0.6 mol / 100 g.
  • the structure of silicone refers to a network-like structure formed by the reaction of silicone compounds with one another or the reaction of a resin and silicone.
  • the amount of Si-H group referred to herein means the number of moles of Si-H structure contained per 100 g of silicone compound, which is the volume of hydrogen gas generated per unit weight of silicone compound by alkaline decomposition method It can be determined by measuring For example, when 122 ml of hydrogen gas is generated per 1 g of the silicone compound at 25 ° C., the amount of Si—H is 0.5 mol / 100 g according to the following formula. 122 ⁇ 273 / (273 + 25) ⁇ 22400 ⁇ 100 ⁇ 0.5 In the silicone compound of the present invention, the amount of aromatic groups in the silicone compound is preferably 10 to 70% by weight.
  • silicone compounds having an aromatic group content in the range of 15 to 60% by weight, and most preferably in the range of 25 to 55% by weight. If the amount of aromatic groups in the silicone compound is less than 10% by weight, the silicone compound may be unevenly distributed, resulting in poor dispersion and poor appearance. If the amount of the aromatic group is more than 70% by weight, the rigidity of the molecule of the silicone compound itself becomes high, so the distribution may be uneven and the appearance may be poor.
  • the amount of aromatic groups here means the ratio in which the aromatic group shown by General formula [10] mentioned above is contained in a silicone compound, and can be calculated
  • Aromatic group weight [A / M] x 100 (% by weight)
  • a and M in the above-mentioned formula represent the following numerical values, respectively.
  • A total molecular weight of all aromatic group moieties represented by general formula [10] contained in one silicone compound molecule
  • M molecular weight of silicone compound
  • the silicone compound used in the present invention has a refractive index at 25 ° C. Is preferably in the range of 1.40 to 1.60.
  • silicone compounds having a refractive index in the range of 1.42 to 1.59, and most preferably in the range of 1.44 to 1.59.
  • the silicone compound is finely dispersed in the aromatic polycarbonate to provide a resin composition having good whitening property and less staining.
  • the silicone compound used in the present invention preferably has a volatilization amount of not more than 18% according to a heat loss method at 105 ° C./3 hours. More preferably, they are silicone compounds whose volatile content is 10% or less. If the amount of volatilization is more than 18%, the resin composition of the present invention is extruded and pelletized, the amount of volatiles from the resin increases, and bubbles are more likely to be generated in the molded product. There is a problem of
  • the silicone compound to be used may be linear or branched as long as the above conditions are satisfied, and the Si—H group may be a side chain in the molecular structure, an end, or a branch. It is possible to use various compounds having one or more points.
  • the structure of a silicone compound containing a Si—H group in the molecule is constituted by arbitrarily combining four types of siloxane units shown below.
  • M unit (CH 3 ) 3 SiO 1/2 , H (CH 3 ) 2 SiO 1/2 , H 2 (CH 3 ) SiO 1/2 , (CH 3 ) 2 (CH 2 CHCH) SiO 1/2
  • monofunctional siloxane units D such as (CH 3 ) 2 (C 6 H 5 ) SiO 1/2 , (CH 3 ) (C 6 H 5 ) (CH 2 CHCH) SiO 1/2, etc .: (CH 3) ) 2 SiO, H (CH 3 ) SiO, H 2 SiO, H (C 6 H 5 ) SiO, (CH 3 ) (CH 2 CH CH) SiO, (C 6 H 5 ) 2 SiO etc
  • T unit (CH 3 ) SiO 3/2 , (C 3 H 7 ) SiO 3/2 , HSiO 3/2 , (CH 2 CHCH) SiO 3
  • preferred structures of the silicone compound are M m D n , M m T p , M m D n T p , and M m D n Q q , and more preferable structures are M m D n or M m D n It is T p .
  • the coefficients m, n, p and q in the above symbolic formula are integers representing the degree of polymerization of each siloxane unit.
  • the attached siloxane unit may be two or more kinds of siloxane units different from each other in a hydrogen atom to be bonded or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group.
  • the sum of the coefficients in each of the equations is the average degree of polymerization of the silicone compound.
  • the average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 4 to 80, and still more preferably in the range of 5 to 60.
  • the degree of polymerization is less than 3, since the volatility of the silicone compound itself is high, there is a problem that the volatile component from the resin tends to be large at the time of processing of the resin composition containing this silicone compound. If the degree of polymerization is greater than 150, the flame retardancy and transparency of the resin composition containing the silicone compound tend to be insufficient.
  • Each of the above-mentioned silicone compounds may be used alone, or two or more of them may be used in combination.
  • Such silicone compounds having a Si-H bond can be produced by methods known per se.
  • the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-produced hydrochloric acid and low boiling components.
  • a silicone oil having a hydrocarbon group having 1 to 20 carbon atoms which may have an Si-H bond, an aromatic group represented by the general formula [10], or another hetero atom-containing functional group in the molecule, cyclic In the case of using siloxane or alkoxysilane as a starting material, an acid catalyst such as hydrochloric acid, sulfuric acid or methanesulfonic acid is used, and water for hydrolysis is optionally added to promote polymerization reaction, The target silicone compound can be obtained by similarly removing the used acid catalyst and low boiling point component.
  • siloxane units M of the silicone compound containing Si-H groups represented by the following structural formula, M H, D, D H , D ⁇ 2, T, T ⁇ (except M: (CH 3) 3 SiO 1 / 2 M H: H (CH 3 ) 2 SiO 1/2 D: (CH 3) 2 SiOD H: H (CH 3) SiOD ⁇ 2: (C 6 H 5) 2 SiT: (CH 3) SiO 3/2 T ⁇ : (C 6 H 5 ) SiO 3/2 ), and the average number of each siloxane unit per molecule is m, m h , d, d h , d p 2 , t, t p and When it does, it is preferable to satisfy all of the following relational expressions.
  • the content of the silicone compound used in the present invention is preferably 0.1 to 7 parts by weight, more preferably 0.1 to 4 parts by weight, still more preferably 0.1 to 7 parts by weight, per 100 parts by weight of component A. 2 parts by weight, most preferably 0.1 to 1 part by weight. If the content is too large, the heat resistance of the resin is lowered, and there is a problem that gas is easily generated during processing. If the content is too small, there is a problem that flame retardancy is not exhibited.
  • the resin composition of the present invention preferably contains a fluorine-containing anti-dropping agent (component C). By containing this fluorine-containing anti-dropping agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.
  • fluorine-containing anti-dripping agent examples include fluorine-containing polymers having fibril-forming ability, and such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). And the like, partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.
  • PTFE polytetrafluoroethylene
  • the molecular weight of the fibril-forming PTFE has an extremely high molecular weight, and tends to bond the PTFE to form a fiber by an external action such as shear force.
  • the molecular weight thereof is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in number average molecular weight determined from the standard specific gravity.
  • Such PTFE may be used in the form of an aqueous dispersion in addition to the solid form. It is also possible to use a PTFE mixture in the form of a mixture with other resins in order to improve the dispersibility in the resin and to obtain good flame retardancy and mechanical properties, as well as such fibril-forming PTFE. is there.
  • Teflon (registered trademark) 6J of Mitsui-Dupont Fluorochemicals Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd., and the like can be mentioned.
  • commercially available aqueous dispersions of PTFE include Fluon AD-1 and AD-936 manufactured by Asahi IC I-Furo Polymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui Dupont Floro Representative examples thereof include Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. and the like.
  • the proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. If the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved.
  • the proportion of the component C indicates the net amount of the anti-dripping agent, and in the case of the mixed form of PTFE, the net amount of PTFE.
  • the content of component C is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1.5 parts by weight, and still more preferably 0.1 to 1 parts by weight with respect to 100 parts by weight of component A. . If the amount of the anti-drip agent is too small beyond the above range, the flame retardancy may be insufficient. On the other hand, when the anti-drip agent exceeds the above range and is too much, not only PTFE may be deposited on the surface of the molded article to cause appearance defects, but it is not preferable because it leads to cost increase of the resin composition.
  • UV absorber> Specific examples of UV absorbers used as component D of the present invention include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-octoxybenzophenone.
  • 2-hydroxy-4-benzyloxybenzophenone 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-) Methoxyphenyl) methane, 2-hydroxy-4-n-dodecylo Examples include xybensophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.
  • the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as benzotriazole-based compounds.
  • the UV absorber is specifically a hydroxyphenyl triazine type, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol , 2- (4,6-Diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) And the like.
  • 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol 2- (4, 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol
  • the phenyl group of the above exemplified compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl
  • the UV absorber is specifically a cyclic imino ester type, for example, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1) And -benzoxazin-4-one), and 2,2'-p, p'-diphenylene bis (3,1-benzoxazin-4-one) and the like.
  • UV absorbers include cyanoacrylates such as 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.
  • the above-mentioned ultraviolet absorber takes such a structure as a monomer compound capable of radical polymerization, and thus the amount of such an ultraviolet-absorbing monomer and / or a light-stable monomer and a single amount of alkyl (meth) acrylate etc.
  • UV absorber It may be a polymer type UV absorber copolymerized with the body.
  • the UV absorbing monomer compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of (meth) acrylic acid ester are suitably exemplified.
  • Ru Among the above, benzotriazole-based and hydroxyphenyltriazine-based ones are preferable in view of ultraviolet light absorbing ability, and cyclic imino ester-based ones and cyanoacrylate-based ones are preferable in view of heat resistance and hue.
  • Chemi-Pur Chemical Co., Ltd. “Chemisorb 79”, BASF Japan Ltd. “Tinuvin 234” and the like can be mentioned.
  • the UV absorbers may be used alone or in combination of two or more.
  • the content of the component D is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 parts by weight, still more preferably 0.05 to 1 parts by weight, particularly preferably 100 parts by weight of the resin component. Is 0.05 to 0.5 parts by weight. If the content is less than 0.01 parts by weight, the weather resistance may not be sufficient, and if it exceeds 3 parts by weight, the flame retardancy may not be sufficient.
  • E1 Phosphorus-based stabilizer examples include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphines.
  • phosphite compounds for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert
  • phosphite compound one having a cyclic structure by reacting with a dihydric phenol can be used.
  • 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite 2,2'-methylenebis (4,6-di-tert- Examples are butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.
  • tributyl phosphate trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monooroxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, preferably triphenyl phosphate and trimethyl phosphate.
  • dimethyl benzenephosphonate dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned.
  • tertiary phosphines triethyl phosphine, tripropyl phosphine, tributyl phosphine, trioctyl phosphine, triamyl phosphine, dimethylphenyl phosphine, dibutylphenyl phosphine, diphenylmethyl phosphine, diphenyl octyl phosphine, triphenyl phosphine, tri-p-tolyl Phosphine, trinaphthyl phosphine, diphenylbenzyl phosphine and the like are exemplified.
  • Particularly preferred tertiary phosphines are triphenyl phosphines.
  • the above-mentioned phosphorus stabilizers can be used alone or in combination of two or more.
  • phosphonite compounds or phosphite compounds represented by the following general formula [14] are preferable.
  • R and R ′ each represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.
  • tetrakis (2,4-di-tert-butylphenyl) -biphenylene diphosphonite is preferable as the phosphonite compound, and the stabilizer based on the phosphonite is Sandostab P-EPQ (trademark, manufactured by Clariant) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), both of which are available.
  • more preferable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis ⁇ 2,4-bis (1-methyl-1-phenylethyl) phenyl ⁇ pentaerythritol diphosphite.
  • Distearyl pentaerythritol diphosphite is commercially available as Adekastab PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP 681 S (trademark, manufactured by Johoku Chemical Co., Ltd.), and any of them can be used.
  • Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is exemplified by Adekastab PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox They are commercially available as P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and all of them can be used.
  • Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as Adekastab PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used.
  • Adekastab PEP-36 trademark, manufactured by Asahi Denka Kogyo Co., Ltd.
  • bis ⁇ 2,4-bis (1-methyl-1-phenylethyl) phenyl ⁇ pentaerythritol diphosphite is exemplified by Adekastab PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), and Doverphos S-9228 (trademark) Commercially available from Dover Chemical Company, Inc., all of which can be used.
  • hindered phenol compound various compounds which are usually blended in a resin can be used.
  • hindered phenol compounds for example, ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol
  • 4-hydroxyphenyl) propionate, and 3,9-bis [2- ⁇ 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] -2,4 , 8, 10-tetraoxaspiro [5, 5] undecane is preferably used.
  • a phosphorus-based stabilizer or a hindered phenol-based antioxidant be blended, and their combined use is more preferable.
  • the content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.001 to 3 parts by weight, more preferably 0.005 to 2 parts by weight, still more preferably 0. It is 01 to 1 part by weight.
  • 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol-based antioxidant are blended with 100 parts by weight of the component A. More preferable.
  • (E3) Release Agent It is preferable to further add a release agent to the resin composition of the present invention for the purpose of improving the productivity at the time of molding and reducing the distortion of the molded product.
  • a release agent for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., those modified with functional group containing compounds such as acid modified can be used), silicone compounds, fluorine compounds ( Fluorine oil represented by polyfluoroalkyl ether etc.), paraffin wax, beeswax etc. can be mentioned.
  • fatty acid esters are mentioned as preferable release agents.
  • Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids.
  • the aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having two or more valences.
  • the carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30.
  • Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol.
  • Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, mannitol and the like. In the fatty acid ester of the present invention, polyhydric alcohols are more preferred.
  • the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms.
  • the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as eicosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid
  • aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils represented by beef tallow and pork fat and natural fats and oils such as vegetable fats and oils represented by palm oil and sunflower oil
  • these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Therefore, aliphatic carboxylic acids produced from such natural oils and fats and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used also in the production of the fatty acid ester of the present invention.
  • the fatty acid ester of the present invention may be either a partial ester or a full ester (full ester). However, partial esters usually have a high hydroxyl value and easily cause decomposition of the resin at high temperatures, and so are preferably full esters.
  • the acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12, from the viewpoint of thermal stability.
  • the acid value may be substantially zero.
  • the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30.
  • the iodine value is preferably 10 or less. The iodine value can be substantially zero.
  • the content of the releasing agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 parts by weight, and still more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of the component A. is there.
  • the resin composition has good releasability and releasability.
  • such amounts of fatty acid esters provide flame retardant resin compositions having good releasability and releasability without compromising good hue.
  • the flame retardant resin composition of the present invention may also contain other thermal stabilizers other than the above-mentioned phosphorus stabilizers and hindered phenol antioxidants.
  • Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both.
  • Such other heat stabilizers include, for example, lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one with o-xylene (such stabilizers The details of are described preferably in JP-A-7-233160).
  • Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Furthermore, stabilizers obtained by mixing the compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Such premixed stabilizers can also be utilized in the present invention.
  • the amount of the lactone stabilizer blended is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the component A.
  • stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotomolding.
  • the amount of the sulfur-containing stabilizer blended is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the component A.
  • the resin composition of the present invention can further provide a molded article which contains various dyes and pigments and expresses various design properties.
  • Dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Dioxazine dyes, isoindolinone dyes, phthalocyanine dyes and the like can be mentioned.
  • the resin composition of this invention can also mix
  • the fluorescent brightening agent is not particularly limited as long as it is used to improve the color tone of a resin or the like to white or bluish white.
  • An imidazole type, a benzoxazole type, a naphthalimide type, a rhodamine type, a coumarin type, an oxazine type compound etc. are mentioned. Specific examples thereof include CI Fluorescent Brightener 219: 1, Eastman Chemical Co., Ltd. EASTOBRITE OB-1, and Showa Chemical Co., Ltd. “Hakkol PSR”.
  • the fluorescent whitening agent has the function of absorbing the energy of the ultraviolet portion of light and emitting the energy to the visible portion.
  • the content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, and more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the resin component.
  • the effect of improving the color tone of the composition is small even if it exceeds 0.1 parts by weight.
  • the resin composition of the present invention can contain a compound having heat ray absorbing ability.
  • Such compounds include phthalocyanine-based near-infrared absorbers, ATO, ITO, iridium oxide and ruthenium oxide, metal oxide-based near-infrared absorbers such as immonium oxide and titanium oxide, lanthanum boride, cerium boride and tungsten boride etc.
  • group and a tungsten oxide type near-infrared absorber, and a carbon filler are illustrated suitably.
  • a phthalocyanine-based near-infrared absorber for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available.
  • the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene and the like, with preference given to carbon black and graphite. These can be used alone or in combination of two or more.
  • the content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and more preferably 0.001 to 0. 100 parts by weight based on 100 parts by weight of the resin component. 07 parts by weight is more preferred.
  • the content of the metal oxide near infrared absorber, the metal boride near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention, 0.5 The range of ⁇ 100 ppm is more preferable.
  • a light diffusing agent can be blended into the resin composition of the present invention to impart a light diffusing effect.
  • light diffusing agents include polymer particles, inorganic particles having a low refractive index such as calcium carbonate, and composites of these.
  • Such polymer particles are particles already known as a light diffusing agent for polycarbonate resin. More preferably, acrylic crosslinked particles having a particle diameter of several ⁇ m and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified.
  • the shape of the light diffusing agent include a sphere, a disc, a pillar, and an amorphous.
  • Such spheres need not be perfect spheres, but include those that are deformed, and such pillars include cubes.
  • the preferred light diffusing agent is spherical, and its particle size is preferably as uniform as possible.
  • the content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the resin component.
  • 2 or more types of light diffusing agents can be used together.
  • the resin composition of the present invention can be blended with a white pigment for high light reflection to give a light reflection effect.
  • a white pigment titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferable.
  • the content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight based on 100 parts by weight of the resin component.
  • two or more kinds of white pigments for high light reflection can be used in combination.
  • the resin composition of the present invention may be required to have antistatic properties, and in such a case, it is preferable to include an antistatic agent.
  • antistatic agents include, for example, (1) arylsulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and phosphonium tetrafluoroborate salts And boric acid phosphonium salts.
  • the content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably 1 part by weight per 100 parts by weight of the resin component. .5 to 3 parts by weight
  • the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonic acid alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above.
  • examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid.
  • the content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably 0 based on 100 parts by weight of the resin component. It is .005 to 0.2 parts by weight.
  • alkali metal salts such as potassium, cesium and rubidium are preferred.
  • the antistatic agent examples include (3) ammonium ammonium sulfonates and organic sulfonic acid ammonium salts such as ammonium arylsulfonic acid salts.
  • the appropriate amount of the ammonium salt is 0.05 parts by weight or less based on 100 parts by weight of the resin component.
  • the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as its component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of the resin component.
  • (E11) Filler In the resin composition of the present invention, various fillers known as reinforcing fillers can be blended. As such a filler, various fibrous fillers, plate fillers and granular fillers can be used.
  • the fibrous filler is in the form of fiber (in the form of a rod, needle, or the axis of which extends in a plurality of directions), and the sheet filler is in the form of a plate (surface And the like, and the plate having a curve).
  • the particulate filler is a filler of other shapes including irregular shapes.
  • the fibrous or plate-like shape is often apparent from the observation of the shape of the filler, but as a difference from, for example, so-called indeterminate form, those having an aspect ratio of 3 or more can be said to be fibrous or plate-like.
  • the plate-like filler examples include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-like fillers obtained by surface-coating such fillers with different materials such as metals and metal oxides. Materials are preferably exemplified.
  • the particle size is preferably in the range of 0.1 to 300 ⁇ m.
  • This particle size refers to the median diameter (D50) of the particle size distribution measured by X-ray transmission method, one of the liquid phase sedimentation methods, in the region up to about 10 ⁇ m, and the laser diffraction in the region of 10 to 50 ⁇ m
  • the value according to the median diameter (D50) of the particle size distribution measured by the scattering method which is a value by vibration sieving in the region of 50 to 300 ⁇ m.
  • the particle size is the particle size in the resin composition.
  • the plate-like filler may be surface-treated with various silane based, titanate based, aluminate based, and zirconate based coupling agents, and also olefin based resins, styrene based resins, acrylic based resins, polyester based resins It may be a granulated material which is subjected to a convergence treatment or compression treatment with various resins such as an epoxy resin and a urethane resin or a higher fatty acid ester.
  • the fibrous filler preferably has a fiber diameter in the range of 0.1 to 20 ⁇ m.
  • the upper limit of the fiber diameter is more preferably 13 ⁇ m, further preferably 10 ⁇ m.
  • the lower limit of the fiber diameter is preferably 1 ⁇ m.
  • the fiber diameter herein refers to the number average fiber diameter.
  • the number average fiber diameter may be determined by dissolving the molded product in a solvent or scanning the residue collected after the resin is decomposed with the basic compound, and the ashing residue collected after ashing in a crucible. It is a value calculated from an image observed by an electron microscope.
  • a fibrous filler for example, glass fiber, flat cross section glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker Fibrous inorganic fillers such as aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, sonotolite, palygorskite (attapulgite), and sepiolite, heat-resistant organic fibers such as aramid fibers, polyimide fibers and polybenzthiazole fibers Fibrous heat-resistant organic fillers represented by the above, and fibrous fillers coated with different fillers such as metals and metal oxides on these fillers It is exemplified.
  • a metal coating glass fiber, a metal coating glass flake, a titanium oxide coating glass flake, a metal coating carbon fiber etc. are illustrated, for example.
  • plating methods for example, electrolytic plating, electroless plating, hot-dip plating, etc.
  • vacuum evaporation method, ion plating method for example, thermal CVD, MOCVD, plasma CVD, etc.
  • PVD method sputtering method etc.
  • the fibrous filler refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more.
  • the upper limit of the aspect ratio is about 10,000, preferably 200.
  • the aspect ratio of such a filler is the value in the resin composition.
  • the flat cross section glass fiber means that the average value of the major axis of the fiber cross section is 10 to 50 ⁇ m, preferably 15 to 40 ⁇ m, more preferably 20 to 35 ⁇ m, and the average value of the major axis to minor axis ratio (major axis / minor axis) is 1 Glass fibers of 5 to 8, preferably 2 to 6, more preferably 2.5 to 5;
  • the fibrous filler may also be surface-treated with various coupling agents in the same manner as the above-mentioned plate-like filler, may be converged with various resins, etc., and may be granulated by compression treatment.
  • the content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less based on 100 parts by weight of the resin component.
  • (E12) Other Resins and Elastomers In the resin composition of the present invention, a small proportion of other resins or elastomers may be used as long as the effects of the present invention are exhibited, instead of part of the resin component of the A component. You can also.
  • the blending amount of the other resin and elastomer is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less in the total 100% by weight of the component A.
  • polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins And resins such as phenol resin and epoxy resin.
  • elastomer for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, core shell type elastomer MBS (methyl methacrylate / styrene / butadiene) Rubber, MB (methyl methacrylate / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber and the like can be mentioned.
  • isobutylene / isoprene rubber for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, core shell type elastomer MBS (methyl methacrylate / styrene / buta
  • any method is adopted to produce the resin composition of the present invention. For example, after sufficiently mixing Component A, Component B and optionally other components using a V-blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc., respectively, and then sufficiently mixing them, an extrusion granulator, if necessary. And granulation using a briquetting machine or the like, followed by melt-kneading with a melt-kneader represented by a vent type twin-screw router, and pelletizing with equipment such as a pelletizer.
  • the PC-POS copolymer in the present invention can be pelletized by melt-kneading using an extruder such as a single screw extruder or a twin screw extruder.
  • an extruder such as a single screw extruder or a twin screw extruder.
  • the various flame retardants, reinforcing fillers and additives described above can also be blended.
  • the resin composition of the present invention can usually be molded by injection molding such pellets.
  • injection molding it is also possible to manufacture by a hot runner which enables runnerless as well as a usual cold runner type molding method.
  • injection molding not only ordinary molding methods but also gas assisted injection molding, injection compression molding, super high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (super It is possible to use molding methods such as rapid heating / cooling mold forming, insulation mold forming and in-mold remelt forming, and combinations thereof, and the like, including those utilizing critical fluid.
  • decorative coating As surface treatment, decorative coating, hard coat, water repellent / oil repellent coat, hydrophilic coat, ultraviolet ray absorbing coat, infrared ray absorbing coat, electromagnetic wave absorbing coat, heat generation coat, antistatic coat, antistatic coat, conductive coat, and meta
  • Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed.
  • the PC-POS copolymer in the present invention can usually be produced by injection molding the pellets produced as described above to produce various products. Furthermore, it is also possible to make the resin melt-kneaded by an extruder directly into a sheet, a film, a profiled extrusion molded article, a direct blow molded article, and an injection molded article without passing through pellets.
  • injection molding injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection of a supercritical fluid), insert molding, as well as ordinary molding methods according to the purpose as appropriate.
  • Molded articles can be obtained using injection molding methods such as in-mold coating molding, insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding.
  • injection molding methods such as in-mold coating molding, insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding.
  • the advantages of these various molding methods are already widely known.
  • either cold runner method or hot runner method can be selected.
  • the PC-POS copolymer in the present invention can also be used in the form of various profile extrusions, sheets, films and the like by extrusion molding. Further, an inflation method, a calendar method, a casting method and the like can be used to form a sheet and a film. It is also possible to form a heat-shrinkable tube by subjecting it to a specific drawing operation. Further, the PC-POS copolymer of the present invention can be formed into a molded article by rotational molding, blow molding or the like.
  • a new layer is formed on the surface layer of resin moldings such as deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It is formed, and the method used for normal polycarbonate resin can be applied.
  • Specific examples of the surface treatment include various surface treatments such as a hard coat, a water and oil repellent coat, an ultraviolet ray absorbing coat, an infrared ray absorbing coat, and metalizing (e.g. vapor deposition).
  • a value obtained by measuring the Charpy notched impact strength of the cooled specimen -30 ° C. in compliance with ISO179 is preferably 30 kJ / m 2 or more, 40 kJ / m 2 or more , 50 kJ / m 2 or more, or 60 kJ / m 2 or more.
  • the value obtained by measuring the notched Charpy impact strength of the test piece cooled to ⁇ 50 ° C. is preferably 40 kJ / m 2 or more, more preferably 50 kJ / m 2 or more. Further, the value obtained by measuring the notched Charpy impact strength of the test piece cooled to ⁇ 60 ° C. is preferably 30 kJ / m 2 or more, more preferably 35 kJ / m 2 or more. Further, the value obtained by measuring the notched Charpy impact strength of the test piece cooled to ⁇ 75 ° C. is preferably 22 kJ / m 2 or more, and more preferably 30 kJ / m 2 or more.
  • the copolymer and the resin composition of the present invention have a value obtained by measuring the notched Charpy impact strength of a test piece cooled to -30 ° C according to ISO 179 after predetermined painting, preferably at 40 kJ / m 2 or more And more preferably 45 kJ / m 2 or more.
  • the value obtained by measuring the Charpy notched impact strength of a given after painting ISO179 test piece was cooled to to -50 ° C. compliant is, preferably 10 kJ / m 2 or more, more preferably 20 kJ / m 2 or more, More preferably, it is 30 kJ / m 2 or more.
  • the copolymer of the present invention and the resin composition thereof are based on ASTM D1003 using Haze Meter NDH 2000 manufactured by Nippon Denshi Kogyo Co., Ltd. in terms of total light transmittance and haze at a thickness of 2.0 mm of a three-step plate.
  • the total light transmittance value measured is preferably 80% or less, more preferably 55% or less.
  • the appearance of the obtained three-step plate is characterized in that defects such as streaky appearance defects, marbled appearance defects, yellowing / blacking appearance defects, surface peeling, color unevenness and transmission unevenness are not remarkable.
  • the above-mentioned appearance defects are observed, but the incidence of minor or defects is less than 50%, and more preferably, no particularly noticeable appearance defects are observed.
  • the transparency and the appearance are above the above range, the appearance defect rate is high, and the productivity is not reduced and the application as an exterior material can not be tolerated.
  • the copolymer of the present invention and the composition thereof are preferably such that only minute cracks of about 1 to 3 mm are formed in the test piece in the following chemical resistance test, and more preferably there is no change in visual appearance.
  • a resin composition containing the polycarbonate-polydiorganosiloxane copolymer of the present invention an ISO dumbbell-shaped tensile specimen obtained by injection molding and having a width of 10 mm, a length of 80 mm, a total length of 150 and a thickness of 4 mm is heat-treated at 120 ° C for 90 minutes Then, it was fixed to the three-point bending jig shown in FIG. 1, and a strain of 0.4% was applied to the center of the formed piece.
  • the exposed piece was covered with the application section, and 0.5 mL of alkaline detergent non-phosphorus forward (Cevies Co., Ltd.) stock solution was applied, and then kept in a thermostat kept at 40 ° C. for 24 hours. The appearance of the exposed portion of the molded piece taken out was evaluated.
  • alkaline detergent non-phosphorus forward Cosmetics Co., Ltd.
  • the copolymer of the present invention and the composition thereof use a capillary-type rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to ISO 11443 (JIS K 7199), and use Toyo Seiki With a capillary type EF (diameter: 1.0 mm, length: 10.01 mm, L / D: 10), at a furnace temperature of 300 ° C., the value of shear viscosity at a shear rate of 1.22 ⁇ 10 3 sec ⁇ 1 Is 50 to 400 Pa ⁇ s, more preferably 150 to 350 Pa ⁇ s, and particularly preferably 200 to 300 Pa ⁇ s. If it is above the lower limit of this suitable range, practical mechanical strength can be obtained in many fields, and if it is below this upper limit, sufficient resin flowability can be secured in injection molding, so that it supports wide product design specifications. It is possible to
  • the copolymer of the present invention and the resin composition thereof have good low-temperature impact resistance and thin-walled flame retardancy, they are suitable as materials for outdoor structural members for various cold regions, various housing members, and automotive parts. Used for In addition, it is useful for various applications such as various electronic / electric equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transport containers, play equipment and sundries, etc. The effect of is exceptional.
  • Shear viscosity In accordance with ISO 11443 (JIS K 7199), a capillary-type rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used as a capillary, capillary type EF (diameter: 1 manufactured by Toyo Seiki Seisakusho Co., Ltd.). The shear viscosity at a shear rate of 1.22 ⁇ 10 3 sec ⁇ 1 was determined at a furnace temperature of 300 ° C. using a .0 mm, length: 10.01 mm, L / D: 10). The obtained pellet was subjected to hot air drying at 120 ° C. for 5 hours, and used as a sample.
  • An ultra-thin section is prepared by cutting perpendicularly to the resin flow direction using UC 6), and is attached to a grid (EM FINE GRID No. 2632 F-200-CU 100PC / CA manufactured by Nippon Denshi Co., Ltd.) Using a TEM JEM-2100 manufactured by Nippon Denshi Co., Ltd., observation was made at an acceleration voltage of 200 kV. The observation magnification was 20,000 times.
  • the obtained microphotograph is subjected to image analysis software Win ROOF Ver.
  • Particle analysis was performed using 6.6 (Mitani Shoji Co., Ltd.) to obtain the average size and particle size distribution (frequency distribution) of the polydiorganosiloxane domains in the sample flakes.
  • the size of each domain the maximum major axis (length when any two points on the outer contour of the particle were selected so as to maximize the length between them) was used.
  • the same analysis was performed on five sample sections, and the average value was taken as the value of each sample.
  • the exposed piece was covered with the application section, and 0.5 mL of an alkaline detergent non-phosphorus forward (Shibayashi Co., Ltd.) stock solution was applied, and then kept in a thermostat kept at 40 ° C. for 24 hours.
  • the appearance of the exposed portion of the molded piece taken out was evaluated.
  • ⁇ No change in visual appearance
  • ⁇ Only fine cracks (1 to 3 mm in length).
  • ⁇ There is a crack (3 to less than 7 mm in length).
  • X There are a plurality of large cracks (7 mm or more in length) or breakage.
  • the value of the average repeating number p + q of the dimethylsiloxane unit was evaluated by 1 H-NMR measurement.
  • the organic phase is separated, diluted with methylene chloride and washed with water, then made acidic with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as ion exchanged water, it is put into a kneader covered with warm water
  • the methylene chloride was evaporated while stirring to obtain a powder of PC-POS copolymer. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulating dryer.
  • the viscosity average molecular weight of the obtained PC-POS copolymer was 16,100, and the polydiorganosiloxane component content (POS content) was 12.5 wt%.
  • PC-POS-2 Manufacturing method of PC-POS-2
  • PC-POS- PC-POS-, except that 13354 parts of methylene chloride (9.5 molar equivalents relative to the total amount of dihydric phenol) were added, and 15 minutes after adding 4.2 parts of triethylamine, methylene chloride was not added. It was similar to the production method of 1.
  • the viscosity average molecular weight of the obtained PC-POS copolymer was 15,900, and the polydiorganosiloxane component content was 12.5 wt%.
  • PC-POS-1 Manufacturing method of PC-POS-10
  • the results of PC-POS-1 were as follows except that 19680 parts of methylene chloride (14 molar equivalents relative to the total amount of dihydric phenol) were added, and 15 minutes after the addition of 4.2 parts of triethylamine, no methylene chloride was added. It was the same as the manufacturing method.
  • the viscosity average molecular weight of the obtained PC-POS copolymer was 15,800, and the polydiorganosiloxane component content was 12.5 wt%.
  • PC-1 Linear aromatic polycarbonate resin powder having a solution viscosity and a molecular weight of 23,900 having a repeating skeleton of 2,2-bis (4-hydroxyphenyl) propane (Panalite L-1250WP manufactured by Teijin Limited).
  • Example 1 Tris (2,4-di-tert-butylphenyl) phosphite (BASF (stock) relative to 100 parts by weight of polycarbonate resin of 33% by weight of PC-POS-1 and 67% by weight of PC-1 obtained in Preparation Example Made): Irgafos 168) mixed to 300 ppm, and then using a vented twin screw extruder (manufactured by Technobel Co., Ltd., KZW 15-25 MG), discharge amount 2.5 kg / h, screw rotation speed 200 rpm The extrusion temperature was pelletized by melting and kneading at 270 ° C.
  • BASF stock
  • Examples 2 to 10 and Comparative Examples 1 to 8 and 11 The resin compositions of Examples 2 to 10 and Comparative Examples 1 to 8 were produced in the same manner as Example 1 except that the type of PC-POS copolymer used and / or the weight ratio of the blend were changed, and The same evaluation as in Example 1 was performed. The results are shown in Table 2.
  • Comparative Example 9 After hot-air drying PC-POS-15 at 120 ° C for 5 hours, using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.), molding temperature 290 ° C, mold temperature 80 ° C, molding cycle A molded piece having a width of 10 mm, a length of 80 mm and a thickness of 4.0 mm was molded in 40 seconds. The produced injection-molded piece was obtained.
  • JSW J-75EIII manufactured by Japan Steel Works, Ltd.
  • Comparative Example 10 The same operation and evaluation as in Comparative Example 9 were performed except that PC-POS-15 was changed to PC-POS-16. The results are shown in Table 2.
  • Component B flame retardant
  • B-1 Perfluorobutanesulfonic acid potassium salt (Megafuck F-114P (trade name) manufactured by Dainippon Ink and Chemicals, Inc.)
  • B-2 Phosphoric ester mainly composed of bisphenol A bis (diphenyl phosphate) (CR-841 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
  • B-3 Cyclic phenoxy phosphazene (Otsuka Chemical Co., Ltd. SPB-100 (trade name))
  • the polytetrafluoroethylene-based mixture is a mixture comprising a polytetrafluoroethylene-acrylic copolymer produced by an emulsion polymerization method (polytetrafluoroethylene content: 50% by weight) (Mitsubishi Rayon Co., Ltd.) Made: Metabrene A 3750 (trade name))
  • D ingredient UV absorber
  • D-1 UV absorber (manufactured by BASF: TINUVIN 234 (trade name))
  • SL900 Fatty acid ester-based mold release agent (manufactured by Riken Vitamin Co., Ltd .; Rikemar SL 900 (trade name))
  • irg 1076 Phenolic heat stabilizer (Ciba Specialty Chemicals K.K .; IRGANOX 1076 (trade name))
  • irg 168 Phosphorus-based heat stabilizer (Ciba Specialty Chemicals K.K .; IRGANOX 1076 (trade name))
  • the strand was extruded under the conditions of cylinder temperature and die temperature of 280 ° C., screw rotation speed of 150 rpm, discharge amount of 20 kg / h, and vent suction degree of 3 kPa, cooled in a water bath, strand cut with a pelletizer and pelletized.
  • the various evaluation results are shown in Table 3 and Table 4.
  • Comparative Example 12 in which the content of the polyorganosiloxane block in the component A is less than 2.5% by weight is inferior in low temperature impact resistance.
  • Comparative Example 13 in which the content of the polyorganosiloxane block in the component A is more than 8.0% by weight, and in Comparative Example 6 in which the number of domains having a maximum length of 80 nm or more is 20 or more, appearance defects occur and flame retardancy It is inferior to.
  • Comparative Examples 14, 15 and 17 which do not contain a domain having a maximum length of 80 nm or more are inferior in low-temperature impact resistance.
  • Comparative Example 18 containing no polycarbonate-polydiorganosiloxane copolymer is inferior in low temperature impact resistance.
  • Examples 21-22, Comparative Examples 19-23 The components A to D except B-2 of the component B and the various additives shown in Table 5 are weighed, uniformly mixed using a blender, and the mixture is fed from the first feed port of the vented twin-screw extruder. The mixture was supplied and melt-kneaded to obtain pellets.
  • the various additives to be used were preliminarily mixed with a polycarbonate resin in advance with a concentration of 10 to 100 times the amount of each compound as a standard, and then the whole mixture was mixed with a blender.
  • Component B-2 is heated to 80 ° C. using a liquid injection apparatus (Fuji Techno Industries, Ltd.
  • HYM-JS-08 using a third supply port (first supply port and vent exhaust in the middle of the cylinder) From the position with the mouth, each was fed to the extruder at a predetermined ratio.
  • the vent type twin-screw extruder used Japan Steel Works TEX30 alpha-38.5 BW-3 V (diameter 30 mm diameter).
  • the strand was extruded under the conditions of cylinder temperature and die temperature of 280 ° C., screw rotation speed of 150 rpm, discharge amount of 20 kg / h, degree of vacuum of vent 3 kPa, cooled in a water bath, strand cut with a pelletizer and pelletized.
  • Table 5 Various evaluation results are shown in Table 5.
  • compositions of Examples 21 and 22 have good low temperature impact resistance and thin wall flame retardancy of 1.0 mmV-0.
  • Comparative Example 19 in which the content of the polyorganosiloxane block in the component A is less than 2.5% by weight, and Comparative Examples 21 and 22 in which the average domain size is smaller than 30 nm are inferior in low-temperature impact resistance.
  • Comparative Example 20 in which the B component is excessive is inferior in low temperature impact resistance and flame retardancy.
  • Comparative Example 23 which does not contain a polycarbonate-polydiorganosiloxane copolymer is inferior in low temperature impact resistance.
  • Examples 23-25, Comparative Examples 24-26 The components A to D and various additives were weighed according to the composition shown in Table 6, mixed uniformly using a blender, and melt-kneaded using a vented twin-screw extruder to obtain pellets.
  • the various additives to be used were preliminarily mixed with a polycarbonate resin in advance with a concentration of 10 to 100 times the amount of each compound as a standard, and then the whole mixture was mixed with a blender.
  • KTX-30 (diameter 30 mm ⁇ ) was used as a vented twin-screw extruder.
  • the strand was extruded under the conditions of cylinder temperature and die temperature of 280 ° C., screw rotation speed of 150 rpm, discharge amount of 20 kg / h, and vent suction degree of 3 kPa, cooled in a water bath, strand cut with a pelletizer and pelletized.
  • Various evaluation results are shown in Table 6.
  • compositions of Examples 23-25 have good low temperature impact resistance and thin wall flame retardancy of 1.0 mmV-0.
  • Comparative Example 24 in which the content of the polyorganosiloxane block in the component A is less than 2.5% by weight, Comparative Example 25 in which the average domain size is smaller than 30 nm, and Comparative Example 26 containing no polycarbonate-polydiorganosiloxane copolymer Low temperature impact resistance is poor.
  • the copolymer of the present invention or the resin composition thereof By using the copolymer of the present invention or the resin composition thereof, it is recognized that the impact durability after coating and the chemical resistance are compatible while having high impact performance even at extremely low temperatures.
  • the copolymer obtained in the present invention or the resin composition thereof has excellent cryogenic impact resistance and chemical resistance, and further has high coating durability, so it can be used in the field of optical components, electric and electronic devices, It can be widely used in transportation and mobility fields such as automobiles and aircraft. Above all, practicality is high in various housing molded articles which are expected to be exposed to severe environments such as extremely cold environments such as high latitudes, mountain areas, and the sky, high temperature heat treatments, and chemical treatments.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

Le but de la présente invention est de fournir : un copolymère de polycarbonate-polydiorganosiloxane ou une composition de résine de celui-ci qui présente une excellente résistance aux chocs, et, en particulier, une excellente résistance aux chocs à des températures extrêmement basses, ainsi qu'une excellente résistance aux produits chimiques ; et un procédé de production pour la composition de résine. Ce copolymère ou la composition de résine de celui-ci comprend un copolymère de polycarbonate-polydiorganosiloxane et une résine de polycarbonate facultative. Le copolymère comporte une séquence polycarbonate (A-1) et une séquence polydiorganosiloxane (A-2). La teneur en séquence polydiorganosiloxane (A-2) du copolymère ou de la composition de résine de celui-ci varie de 2,5 à 8,0 % en poids. Le copolymère ou la composition de résine de celui-ci est conforme à (i) et (ii) : (i) dans une image d'observation en coupe transversale du copolymère ou de la composition de résine de celui-ci générée à l'aide d'un microscope à faisceau électronique, on compte 1 à 20 domaines dont le plus long diamètre est au moins égal à 80 nm dans une zone mesurant 850 nm carrés (722 500 nm2) ; et (ii) la taille de domaine moyenne varie de 30 à 100 nm.
PCT/JP2018/047367 2017-12-21 2018-12-21 Copolymère de polycarbonate-polydiorganosiloxane, composition de résine de copolymère de polycarbonate-polydiorganosiloxane, et procédé de production d'une composition de résine de copolymère de polycarbonate-polydiorganosiloxane WO2019124556A1 (fr)

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CN201880076044.9A CN111386298B (zh) 2017-12-21 2018-12-21 聚碳酸酯-聚二有机硅氧烷共聚物、其树脂组合物和其制造方法
EP18890638.2A EP3730534B1 (fr) 2017-12-21 2018-12-21 Copolymère de polycarbonate-polydiorganosiloxane, composition de résine de copolymère de polycarbonate-polydiorganosiloxane, et procédé de production d'une composition de résine de copolymère de polycarbonate-polydiorganosiloxane
KR1020207015107A KR102321244B1 (ko) 2017-12-21 2018-12-21 폴리카보네이트-폴리디오르가노실록산 공중합체, 그 수지 조성물, 및 그 제조 방법
US16/956,041 US11414523B2 (en) 2017-12-21 2018-12-21 Polycarbonate-polydiorganosiloxane copolymer, resin composition of polycarbonate-polydiorganosiloxane copolymer, and production method for resin composition of polycarbonate-polydiorganosiloxane copolymer
JP2019560601A JP7055152B2 (ja) 2017-12-21 2018-12-21 ポリカーボネート－ポリジオルガノシロキサン共重合体、その樹脂組成物、およびその製造方法

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WO2022168454A1 (fr) * 2021-02-02 2022-08-11 帝人株式会社 Composition de résine de polycarbonate et article moulé
WO2022260076A1 (fr) * 2021-06-09 2022-12-15 出光興産株式会社 Composition de résine de polycarbonate et article moulé
WO2022260077A1 (fr) * 2021-06-09 2022-12-15 出光興産株式会社 Composition de résine de polycarbonate et article moulé

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EP3719077B1 (fr) * 2019-04-02 2022-09-21 Covestro Deutschland AG Copolycarbonates séquencés contenant du siloxan à faible granulométrie
TWI792048B (zh) * 2020-08-26 2023-02-11 大陸商漢達精密電子（昆山）有限公司 一種高流動性阻燃聚碳酸酯材料及其製品
CN114196001B (zh) * 2022-01-11 2023-09-19 万华化学集团股份有限公司 一种聚碳酸酯-聚有机硅氧烷共聚物、制造方法及包含该共聚物的树脂组合物

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WO2021112259A1 (fr) * 2019-12-06 2021-06-10 出光興産株式会社 Copolymère polycarbonate/polyorganosiloxane et composition de résine comprenant ledit copolymère
WO2022168454A1 (fr) * 2021-02-02 2022-08-11 帝人株式会社 Composition de résine de polycarbonate et article moulé
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US11414523B2 (en) 2022-08-16
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TW201930408A (zh) 2019-08-01
JP7254126B2 (ja) 2023-04-07
EP3730534A4 (fr) 2021-02-24
US20210108033A1 (en) 2021-04-15
EP3730534A1 (fr) 2020-10-28
TWI788490B (zh) 2023-01-01
KR20200068737A (ko) 2020-06-15
EP3730534B1 (fr) 2021-11-10
JP7055152B2 (ja) 2022-04-15
KR102321244B1 (ko) 2021-11-02
CN111386298B (zh) 2023-01-13

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